Fatty oil modified polycarbonate resins and processes for producing same



United States Patent 3357,6 36 FATTY 0E PGLYQAPEGNATE RESLQS ANDlRtlilESSES Fill-l SAME Rudolph i). Deanin, West Hartford, 4Com! and AnnV. Pinter, Morristown, NJ, assignors to Allied Qhemieal gorporation, NewYork, Nfiifi, a corporation of New ion-r No Drawing. Filed May 12,19x51, Ser. No. 169,489 20 Claims. (Cl. 26il13) The present inventionrelates to new and useful polycarbonate resins and processes forpreparing them.

More specifically, the present invention resides in fatty oil modifiedpolycarbonate resins derived from bisphenols having the structure inwhich R is a divalent allrane or saturated alicyclic radical or adivalent aryl or aralkyl radical containing only aromatic unsaturation,R is a monovalent allrane radical and n is an integer from 0 to 4-, andthe derivatives of those bisphenols which contain halogen attached tocarbon in an aroma-tic ring.

conventionally polycarbonate resins are prepared by either phosgenationor trans-esterification. in the phosgenation method phosgene is reactedwith a bisphenoi in an aqueous alkaline medium, preferably in thepresence of a catalyst and a solvent for the polycarbonate resin formed.Alternatively, the phosgene may be reacted with a bisphenol in pyridine,where pyridine acts as'the hydrohalide acceptor and as solvent for thepolycarbonate resin formed, and possibly also as catalyst. Preferablythe solvent function of the pyridine is replaced in whole or in part bythe addition of lower cost solvents. The transesterification methodinvolves the transe sterification of a bisphenol and a carbonic aciddiester, especially diphenyl carbonate. The transesterir'icationreaction is preferably conducted at elevated temperatures and at reducedpressures.

Polycarbonate resins prepared by any of the foregoing methods yield poorcoating compositions, for example, polycarbonate resins prepared by anyof the above procedures and applied by conventional methods as coatingsto aluminum or steel give inflexible coatings having poor adhesion. Whenthese coatings are baked at elevated temperatures (on the order of 206C.) the adhesion is somewhat improved, but the flexibility remains poor.Furthermore, the initial polymer is not soluble enough in common lacquersolvents, nor readily emulsifiable; whfie the final coating is tooreadily attacked by solvents. When the foregoing polycarbonate reactionsare conducted in the presence of a fatty oil the resulting polycarbonateproduct still yields poor coating compositions, for example, whenpolycarbonate resins so prepared are applied by conventional methods ascoatings to aluminum or steel the resulting coatings are cloudy toopaque and are characterized by having poor adhesion unless baked atelevated temperatures.

It is therefore an object of the present invention to provide new anduseful polycarbonate resins and processes for preparing them, whichresins find utility in a wide variety of applications, for example,moldings, films, coatings, etc.

t is a further object of the present invention to prepare new andversatile polycarbonate resins inexpensively and expeditiously.

tis a still further object f the present invention to preparepolycarbonate resins having excellent physical characteristics.

greases ?atented Nov. 1?, i964 It is a particular object of the presentinvention to prepare polycarbonate resins useful in the preparation ofcoating compositions, which resins provide coatings having excellentphysical properties, such as clarhy, impact, flexibility, color, etc.

it is a further object of the present invention to provide novelpolycarbonate resins useful in the preparation of coating compositionswhich exhibit excellent adhesion without the necessity of baking at hightemperatures.

Further objects and advantages of the present invention will appearhereinafter.

According to the present invention we have found that new and usefulpolycarbonate resins may be prepared, accomplishing the foregoingobjects and advantages of the present invention, by (l) reactingtogether from about 10 to about 90 weight percent of a fatty oil andfrom about 90 to about 10 weight percent of a bisphenol, as definedbelow, at a temperature between the melting point and the boiling pointof said bisphenol, (2) reactin the resulting reaction product with anester forming derivative ofcarbonic acid selected from the groupconsisting of phosgene and a carbonic acid diester, and (3) recoveringthe resulting polycarbonate resin.

The reaction between the fatty oil and the bisphenol is conducted atelevated temperatures, and atmospheric pressure may be employed. Thetemperature of reaction may vary between the melting point and theboiling point of the bisphenol, for example, when2,2-(4,4-dihydroxydiphenyl)-propane, also known as p,p'-isopropylidenediphenol, hereinafter referred to as Bis-phenol-A, 'is employed thetemperature may vary between about 157 C. and about 370 (3., dependingupon the purity of the Bisphenol-A. It has been found that forBis-phenol-A the preferred temperature range is between about 275 C.

and about 330 C. The time of the reaction may vary within a wide rangedepending upon reactants and reaction temperatures; generally, however,the reaction is continued until the reaction mass. becomes homogeneous,with at least 5 or 10 minutes being required at the higher temperaturesand at least 4 or 5 hours at the lower temperatures. Extended reactiontimes may be employed without adverse effect, for example, reactiontimes on the order of 10 to 20 hours. The fatty oil bisphenol reactionproduct is preferably prepared from about it) to about 60 weight percentof fatty oil, and correspondingly from about 90 to about 40 Weightpercent of bisphenol, and more preferably being from about 55 to aboutweight percent of bisphenol. After the desired reaction time the entirereaction mass is reacted with either phosgene or a carbonic aciddiester, and the resulting polycarbonate resin separated from thereaction mixture. The fatty oil-bisphenol reaction product is readilyflowable at the temperatures of reaction, viz., between about theboiling point and melting point of the bisphenol. When the product iscooled to room temperature, however, it becomes thick and syrupy. it is,therefore, desirable to dissolve the product in a solvent in order toobtain the preferred ambient temperature viscosity for the polycarbonatereaction. Any solvent regularly used for polycarbonate resins issuitable for this purpose, for example, methylene chloride.

The fatty oil employed in the present invention is a glyceride oil andmay be either of the semi-drying, drying or non-drying type. inaddition, the fatty oil may be saturated or unsaturated, and may beeither of the vegetable, animal, or fish type. The oil itself may beemployed in the present invention or the fatty acid from which the oilis derived plus glycerine may be employed, since when fatty acids arecombined with glycerine they give fatty oil glycerides which are theprincipal constituents of fatty oils, which latter term is intended toinclude fatty acids plus glycerine. Illustrative fatty oils of thevegetable type which may be employed in the present invention are:dehydrated castor oil, linseed oil, perilla oil, soyabean oil, corn oil,cotton seed oil, tall oil, coconut oil, olive oil, peanut oil, sunfloweroil, poppyseed oil, safflower oil, oiticica oil, and tung oil.Illustrative animal and fish oils which may be employed are whale oil,menhaden oil, sar-' dine oil, herring oil, and codliver oil.illustrative fatty acids from which the oil is derived which maybeemployed in combination with glycerine are: lauric acid,

in which R is a divalentalkane or saturated alicyclic radical or adivalent aryl or aralkyl radical containing only aromatic unsaturation,R is a monovalent alkane radical and n is an integer from to 4, and thederivatives of those bisphenols which contain halogen attached to carbonin'an aromatic ring. The polycarbonates of the bisphenols hav ing theabove structure in which each of the two hydroxyl groups is in the4-position of a phenylene radical and are linked through a single carbonatom of a divalent alkane radical, are the preferred bisphenolpolycarbonates reacted with fatty oils in accordance with our invention.

The following are examples of such bisphenols:

(4,4'-dihydroxy-diphenyl -methane,

2,2-(4,4-dihydroxy-diphenyD-propane, (BiSphenol-A),

1,1-(4,4'-dihydroxy-diphenyl) -cyclohexane,

1, l- (4,4'-dihydroxy-3,3 -dimethyl-diphenyl -cyclohexane,

2,2-(2,2-dihydroxy-4,4-di-tent-butyl-diphenyl)propane,

3,4- (4,4'-dihydroxy-diphenyl) -hexane,

V 1,1-(4,4 dihydroxy-diphenyl)-l-phenyl-ethane,

2,2- (4,4-dihydroxy-diphenyl -butane, 2,2- (4,4'-dihydroxy-diphenyl-pentane, 3,3-(4,4-dihydroxy-diphenyl)-pentane,

2,2- (4,4-dihydrox -diphenyl -3-methyl-butane,

as well as the halogen derivatives of those bisphenols, e.g.,

2,2-(4,4'-dihydroxy-3,3-dichloro-diphenyl)-propane,

2,2- (4,4-dihydroxy-3 ,5 ,3 ,5 -tetrabromo-diphenyl) -propane, and

1,4-(4,4'-dihydroxy-dicumyl)-tetrachlorobenzene.

In addition, mixtures of the foregoing bisphenols may be employed.

The polycarbonate resin is prepared by reacting the fatty oil-bisphenolreaction product with either phosgene (phosgenation method) or with acarbonic acid diester (transesterification method) and the resultingpolycarbonate resin separated from the reaction mixture. Thephosgenation method includes the aqueous alkaline procedure and thepyridine procedure.

When the aqueous alkaline procedure is employed the phosgene ispreferably slowly introduced in an aqueous alkaline solution containingthe fatty oil-bisphenol reaction product. The phosgene to fattyoil-bisphenol reaction product ratio is not critical. Practically,however, at least 0.1, mol of phosgene is employed per mol of hisphenolin said reaction product. Due to side reactions of the phosgene, it ispreferred to employ from 1.1 to 2 mols of phosgene per mol of bisphenol.Greater amounts of phosgene may be employed, if desired, but the additional phosgene is merely unconsumed. If less than one mol of phosgeneis employed the fatty oil-bisphenol reaction product is not utilized tothe fullest extent.

The phosgene is preferably introduced into the aqueous alkaline solutionslowly, over a period of time generally on the order of 15 minutes tofour hours. When the reaction is run continuously, naturally thephosgene will be continuously introduced. When all the phosgene has beenadded there generally follows a molecular Weight growth period duringwhich the reaction mixture is stirred and polycarbonate resin grows inmolecular weight.

The temperature of the aqueous alkaline phosgenation reaction may varywithin a wide range, that is, the reaction may be conducted at roomtemperature or lower or higher temperatures as desired. Generallytemperatures from the freezing point to the boiling point of the mixturemay be utilized. It has been found that there is a tendency formolecular weight increase at the higher temperatures. Atmosphericpressure .may be employed.

It is preferred to employ a suitable solvent for the polycarbonate resinin order to retain the polycarbonate in solution, since molecular weightgrowth occurs in solution. If no solvent is employed only low molecularweight polymer is produced and this polymer precipitates. from solutionsubstantially as fastas formed. .The'polyrner should be soluble in thesolvent which is employed,

and the solvent should be inert underthe conditions of the reaction,immiscible in water and have a sutficiently high boiling point to allowfor reaction at elevated temperatures, if desired. Generally speaking,it is preferred to employ a solvent which has a boiling point of 30 C.to C. The solvent is preferably added initially, and

added in amounts so that the final polymeric solution is fluid. Theamount of solvent is not critical, but practicaL' 1y from 0.1 to 50parts by weight of solvent per part of: polycarbonate formed should beused. Typical solvents" include methylene chloride, benzene,cyclohexane, methylcyclohexane, toluene, xylene, chloroform, carbontetrachloride, trichloroethylene, dichloroethane, methylacetate andethylacetate.

It is also preferred in this process to employ acatalytic, amount of acatalyst for the reaction, with any of the.

conventional catalysts being applicable. The catalyst is preferablyemployed in amounts from about 0.05 to about 5.0 percent by weight basedon bisphenol, and it is pre-' ferred to employ a quaternary ammoniumcompound.

Typical catalysts include the following:. quaternary ammonium compounds,such as the halides or hydroxides, for example, benzyl triethyl ammoniumchloride, tetra methyl ammonium hydroxide, benzyl trimethyl ammoniumfluoride, octadecyl triethyl ammonium chloride, dodecyl trimethylammonium chloride, benzyl phenyl dimethyl ammonium chloride, cyclohexyltrimethyl ammonium bromide, etc.; tertiary amines, such astrimethylamine, dimethyl aniline, diethyl aniline, etc. The use of theseand other catalysts will be apparentto one skilled in the art. Thecatalyst may be added either before or after the phosgenation period.

The aqueous alkaline solution may be formed from an alkali metal base,preferably employing an excess of base, such as lithium, sodium, orpotassium hydroxide.

The polycarbonate resin may be recovered from solution by conventionalmeans, for example, anon-solvent for the polycarbonate resin may beadded to the reactionmixture in order to precipitate the polycarbonateresin.

Typical non-solvents include methanol, isopropanol, etc. Other methodsfor recovery of the polycarbonate resin includesteam distillation orevaporation of the solvent.

Potential chain terminators may be employed in the process of thepresent invention in order to limit the molecular Weight. Typical ofsuch compounds are a a U phenol, tertiary butyl phenol, chlorophenol,nonyl alcohol, butyl alcohol, etc.

Various additives may be employed, such as anti-oxidants, and additivesto preferentially react with phosgene decomposition products. Typical ofsuch additives are sodium dithionite, potassium bisulfite, carbonmonoxide,

etc.

In the pyridine procedure pyridine functions as the hydro-halideacceptor, the solvent and in addition possibly as the catalyst. Thephosgene is preferably slowly introduced into a stirred solution of thefatty oil-bisphenol reaction product in pyridine, with a somewhatexothermic reaction ensuing. Preferably pyridine is replaced in itssolvent function by conventional lower cost polycarbonate resinsolvents. The desired solvent may be selected from any of thepolycarbonate resin solvents listed above. Generally at least one mol ofpyridine per mol of bisphenol in the reaction product is required, withthe preferred amount being from about three to about five mols.Additional amounts of pyridine may,

of course, be employed if desired. At some point in the reactionpyridine hydrochloride begins to crystallize out of the mixture. As thestoichiometric amount of phosgene is reached the reaction mixture turnsviscous. The polymer may then be recovered from the reaction mixture byconventional means, for example, by being precipitated by non-solventsfor the polycarbonate resin, such as methanol and isopropanol, or bysteam distillation or evaporation of the solvent. The ratio of phosgeneemployed and thetemperature and pressure of the reaction are the same asin the aqueous alkaline procedure outlined above. In addition, theaforementioned chain terminators and additives may also be employed. Itshould be noted that special care must be taken to wash out all of thepyridine and pyridine hydrochloride from the reaction mixture in orderthat the final precipitated polymer will be free of contamination.

In the transesterification procedure the fatty oil-bisphenol reactionproduct is transesterified witha carbonic acid diester, preferably atelevated temperatures and re duced pressures, with the amount ofcarbonic acid diester not being critical. Practically, however, at least0.1 mol of carbonic acid diester is employed per mol of bisphenol in thefatty oil-bisphenol reaction product. It is preferred to conduct thetransesterification reaction at temperatures of from about 50 C. toabout 320 C., especially from about 120 C. to about 280 C., andpressures up to about 50 millimeters of mercury. The preferred carbonicacid diester is diphenyl carbonate, but others which may be employedinclude the following carbonates: dimethyl; diethyl; dipropyl; dibutyl;diamyl; dioctyl; dicyclohexyl; and di-o,p-tolyl. In the normal operationthe reaction mirture is held under 185 C. at relatively poorer vacuumuntil about 80 to 90 percent of the phenol of condensation has beenremoved. At this point the temperature is raised to above 185 C. andthe. pressure is reduced to high vacuum to drive off remaining phenol.As the reaction proceeds the melt viscosity increases and the molecularweight grows. The polycarbonate resin may be removed from the reactionvessel by conventional means. Catalytic amounts of standardtransesteritication catalysts may be employed, if desired. Preferably,the catalyst is employed in amounts 0.1 to 5 percent based on thebisphenol. Suitable catalysts include lithium, sodium, potassium,calcium, beryllium, magnesium, zinc, cadmium, aluminum, chromium,molybdenum, manganese, iron, cobalt, nickel, copper, silver, mercury,tin, lead, bismuth, antimony, platinum and palladium. These metalliccatalysts may be used in any desired form, such as powder, chips,ribbon, wire, etc. However, the preferred catalysts of the presentinvention are oxides and salts of metals, such as carbonates, chlorides,acetates, borates, or oxides of materials such as magnesium, lead,cobalt, cerium, or antimony. Suitable catalysts of this type include,for example, magnesium oxide, lead diti oxide, cobaltous acetatetetrahydrate, ceric oxide, autimony trioxide, etc.

The polycarbonates obtained by the process of the present invention haveoutstanding properties desired but not obtainable by the conventionalpolycarbonate resins. Typical of the properties of the polycarbonates ofthis invention are:

Drop impact 26-28 inch pounds. Adhesion (tape) No film loss. Mandrel Nocracking. Sward rocker hardness 56.

Gloss Good.

Clarity Clear.

The above tests are described in Physical and Chemical Examination:Paints, Varnishes, Lacquers, Colors. Eleventh Edition, 1950.

One dtiiculty in the use of the prior art coating compositions ofpolycarbonates is the requirement of baking at high temperatures about200 C. in order to attain adhesion and flexibility. Coating compositionsof polycarbonates of the present invention give good adhesion withoutbaking but with driers, or with baking at low temperatures below aboutC. This property is very important, practically and economically, and isdistinctly superior to the conventional polycarbonates. Anotherdifiiculty ith the polycarbonate coating compositions is a coating whichis cloudy to opaque unless baked at high temperatures of 200 C. orhigher; whereas, the coating composition of the present invention givesa clear film without baking. The polycarbonates of the present invention are also quite soluble in common lacquer solvents and readilyemulsifiable.

To illustrate the differences between the polycarbonates of the presentinvention and the conventional polycarbonates, a commercial bisphenolpolycarbonate was solution cast (5 to 20% in methylene chloride) ontosteel plates and showed poor adhesion and flexibility, unless baked athigh temperatures (200 (3.). Moreover, the

initial polycarbonate is sparingly soluble in common lac-' quer solventsand not readily emulsifiable. Further, the final coating, even whenbaked at high temperatures (200 C.), is readilyv attacked by solvents.

To illustrate the importance of first effecting reaction between a fattyoil and the bisphenol, a solution of Bisphenol-A and dehydrated castoroil in methylene chloe ride was phosgenated and the resulting productisolated and redissolved in methylene chloride. This solution was thencast on steel plates and it was found that the resulting coatings werecloudy to opaque and also had poor adhesion to steel unless baked at 200C.v From the foregoing it will be evident that the polycarbonates of thepresent invention have desirable characteristics, particularly thecharacteristic of resulting in a coating of excellent adhesion andflexibility Without baking, a clear coating and good solubility incommon lacquer solvents as well as ready emulsifiability.

The coating compositions of the present invention may be convenientlyprepared by first dissolving the resin component in a volatile organicsolvent and applying the resulting composition to the surface to becoated. Alternatively, since many of the resins of the present inventionare prepared in solvent, for example, methylene chloride, thepolycarbonate resin solution may be directly applied to the surface tobe coated. The coatings may be applied by conventional means, forexample, dipping, brushing, spraying or coating with a doctor blade. Thecoated films have good dryin rates and may thereafter be dried and curedat room temperature or moderately elevated temperature to removesolvent. Optionally, driers maybe added to accelerate drying and curingtime.

The solvent which is employed should be non-reactive and should have asufficiently low boiling point so that it will vaporize from thecomposition when coated onto a substrate in a thin film. Solvents havinga boiling point 7 between about 30 C. and about 175 C. are suitable. Inaddition, mixed solvents may be advantageously employed. Suitablesolvents include, for example, toluene, xylene, various petroleumhydrocarbon distillate fractions, methylene chloride, isopropyl ether,ethyl acetate, methyl ethyl ketone and cyclohexanone.

The amount of solvent used should vary between about 40 to about 95percent by Weight of the total formulation. Below this range theformulation is too viscous to be used eifectively; above it theformulation is too dilute to lay down a coating of adequate thicknessand covering power.

The coating compositions of the present invention may be dried and curedat room temperature or at moderately elevated temperature. If desired,driers may be added to accelerate drying and curing time. Under ordinaryroom temperature conditions without added driers the coatings drytack-free in from about 0.25 to about 0.5 hour, and are completely curedin from about 4 to about 5 days. In addition, the conventional driers inamounts from 7 about 0.08 to about 0.12 percent by weight of the totalExample 1 V 1 Dehydrated castor oil 22.2 grams and Bis-phenol-A 37 gramsare mixed together and heated to 270 C. over a half-hour period, thenheld at 270 C. to 320 C. for one-half hour, and finally cooled to 30 C.over another half-hour period. This reaction product is dissolved in 500cubic centimeters of methylene chloride, and charged into a one-literresin pot containing 31.5 grams of 95 "percent NaOH dissolved in 50cubic centimeters of water, The mixed liquids are stirred under nitrogenflush and reflux condenser, and 6.4 cubic centimeters of 10 percentaqueous solution of benzyl triethyl ammonium chloride catalyst is added.Phosgene gas 27.5 grams is bubbled into the stirred emulsion evenly overa one-hour period, using a cold Water bath to keep the temperature at C.The emulsion is stirred for another hour at 30 C. to complete thereaction. The emulsion is acidified with dilute HCl, and the organiclayer of copolymer dissolved in methylene chloride is separated, driedover calcium chloride, and concentrated by vacuum evaporation at roomtemperature to a viscous solution. When this solution is spread onaluminum and steel panels, evaporated, and oven-dried, the resin formsclear, light-colored, adhesive, flexible, and impact-resistant coatings.When 0.1% cobalt-manganese drier is added to the solution, the coatingscure to'hard, dry coatings retaining all of the above qualities.

Example 2 7 Coconut oil 6.3 grams and Bis-phenol-A 35.9 grams are mixedtogether and heated to 300 C. over a half-hour period, held at 282 C. to330 C. for one-half hour, and cooled to 30 C. over another -minuteperiod. Another 15.4 grams of Bis-phe'nol-A is added, and the mixturephos'genated as in Example 1. The resulting solution of resin inmethylene chloride is Washed with acid and Water, coagulated by slowaddition of acetone with methanol with stirring, filtered, and dried.When this solution is spread on aluminum and steel panels, evaporated,and oven-dried, the resin forms clear, light-colored,

Dehydrated castor oil 22.8 grams and Bis-phenol-A 40 grams are heatedtogether to 270 C. for 30 minutes under a slow stream of nitrogen, thencooled to room temperature. The reaction product is dissolved in 500cubic centimeters of methylene chloride, and 79 grams of pyridine isadded. Phosgene 30 grams is bubbled into the stirred solution over ,aone-hour period, using a cold- Water bath to keep the temperature at 30C. The solution is stirred another 45 minutes at 30 C. to finish the:reaction. The solution is then washed twice with dilute HCl, and oncewith water, then dried over calcium chloride, filtered, and concentratedby vacuum evaporation; When this solution is evaporated on an aluminumbacking, it gives a clear, adhesive, flexible coating. .Baking ontosteel at C., it gives clear, adhesive, tough, hard,

glossy coatings.

Example 4 Dehydrated castor oil 44.5 grams and Bis-phenol-A 60 grams areheated under a stream of nitrogen for 45 min-- utes at 300 C. and thencooled. Diphenyl carbonate 37.6 grams and PbO and ZnO 0.053 gram eachare added as a catalyst and the mixture is heated andstirred undervacuum. The reaction is held for minutes at 20 millimeters and C.,removing most of the phenol. The reaction is continued for 30 additionalminutes at 3.5 millimeters and completed in 30 additional minutes atv200 C. and 1.6 millimeters vacuum during this period. At the end, themolten reaction product is poured put and cooled. When solutionsof theforegoing polycarbonate resin in 90% by weight methylene chloride arecatalyzed with 0.1 percent of cobalt drier and 0.05 per cent manganesedrier and coated on steel panels, resulting coatingsare dry, smooth,clear, amber, adhesive, flexible on mandrel test, Sward hardness 56, anddrop impact .28 inch pounds. 7

Example 5 stirred under nitrogen flush and reflux condenser, and 9.1

cubic centimeters of 10 percent aqueous solution of benzyl triethylammonium chloride catalyst is added. Phosgene gas 27.5 grams is bubbledinto the. stirred emulsion evenly over a one-hour period, using avcoldWater bath to keep the temperature at 30 C. The emulsion is stirred foranother hour at 30 C. to complete the reaction. The emulsion isacidified with dilute HCl, and the organiclayer of copolymer dissolvedin ethylene chloride is separated and precipitated by the rapid additionof 1000 cubic centimeters of methanol to a viscousyellow liquid. Thisliquid is re-dissolved in 5 00 cubic centimeters of methylene chloride,dried over calcium chloride, and concentrated by vacuum evaporation atroom tempera:

ture to a viscous solution. When this solution is-spread =1 illustrativeand not restrictive, the scope of the invention being indicated by theappended claims and all changes which come within the meaning and rangeof equivalency are intended to be embraced therein.

We claim:

1. A polycarbonate resin produced by reacting (1) an ester formingderivative of carbonic acid selected from the group consisting ofphosgene and a carbonic acid diester, and (2) the reaction productobtained by heating a mixture of from about 10 to about 90 weightpercent of a fatty oil and from about 90 to about 10 weight percent of abisphenol selected from the group consisting of bisphenols having thestructure Rn R in which R is a member of the group consisting of thedivalent alkane and saturated alicyclic radicals and the divalent aryland aralkyl radicals containing only aromatic unsaturation, R is amonovalent alkane radical and n is an integer from to 4, and thederivatives of those bisphenols which contain halogen attached to carbonin an aromatic ring, wherein at least 0.1 mol of said ester formingderivative of carbonic acid is employed per mol of the bisphenol.

2. A polycarbonate resin produced by reacting (l) a carbonic aciddiester, and (2) the reaction product obtained by heating a mixture offrom about to about 90 weight percent of a fatty oil and from about 90to about 10 weight percent of a bisphenol selected from the groupconsisting of bisphenols having the structure HO OH Q R v D in which Ris a member of the group consisting of the divalent alkane and saturatedalicyclic radicals and the divalent aryl and aralkyl radicals containingonly aromatic unsaturation, R is a monovalent alkane radical and n is aninteger from 0 to 4, and the derivatives of those bisphenols whichcontain halogen attached to carbon in an aromatic ring wherein at least0.1 mol of said carbonic acid diester is employed per mol of the hisphenol.

3. A polycarbonate resin produced by reacting (1) phosgene and (2) thereaction product obtained by heating a mixture of from about 10 to about90 weight percent of a fatty oil and from about 90 to about 10 weightpercent of a bisphenol selected from the group consisting of bisphenolshaving the structure in which R is a member of the group consisting ofthe divalent alkane and saturated alicyclic radicals and the divalentaryl and araikyl radicals containing only aromatic unsaturation, R is amonovalent aJlrane radical and n is an integer from 0 to 4, and thederivatives of those bisphenols which contain halogen attached to carbonin an aromatic ring, wherein at least 0.1 mol of said phosgene isemployed per mol of the bisphenol.

4. A polycarbonate resin according to claim 3 wherein said bisphenol is2,2-(4,4-dihydrox '-diphenyl)-propane.

5. A polycarbonate resin according to claim 3 wherein said bisphenol is1,4-(4,4'-dihydroXy-dicumyl)-benzene.

6. A polycarbonate resin according to clairn 4 wherein said fatty oil isdehydrated castor oil.

7. A polycarbonate resin according to claim 4 wherein said fatty oil iscoconut oil.

8. A coating composition comprising a polycarbonate resin according toclaim 1 and from about 40 to about percent by weight of a volatileorganic solvent having a boiling point of from about 30 C. to about C.

9. A coating composition comprising a polycarbonate resin according toclaim 2 and from about 40 to about 95 percent by weight of a volatileorganic solvent having a boiling point of from about 30 C. to about 175C.

10. A coating composition comprising a polycarbonate resin according toclaim 3 and from about 40 to about 95 percent by weight of a volatileorganic solvent having a boiling point of from about 30 C. to about 175C.

11. A process for the preparation of a polycarbonate resin whichcomprises (1) reacting together from about 10 to about 90 weight percentof a fatty oil and from about 90 to about 10 weight percent of abisphenol se lected from the group consisting of bisphenols having thestructure in which R is a member of the group consisting of the divalentalkane and saturated alicyclic radicals and the divalent aryl andaralkyl radicals containing only aromatic unsaturation, R is amonovalent alkane radical and n is an integer from 0 to 4, and thederivatives of those bisphenols which contain halogen attached to carbonin HO OH an aromatic ring at a temperature of between the melting,

point and the boiling point of said bisphenol, (2) reacting saidreaction product (1) with at least 0.1 mol of an ester formingderivative of carbonic acid selected from the group consisting ofphosgene and a carbonic acid HO OH in which R is a member of the groupconsisting of the divalent alkane and saturated alicyclic radicals andthe divalent aryl and aralkyl radicals containing only aromaticunsaturation, R' is a monovalent alkane'radical and n is an integer from0 to 4, and the derivatives of those bisphenols which contain halogenattached to carbon in an aromatic ring at a temperature of between themelting point and the boiling point of said bisphenol, (2) reacting saidreaction product (1) with at least 0.1 mol of a carbonic acid diesterper mol of bisphenol at a temperature of from about 50 C. to about 320C., and (3) recovering the polycarbonate resin from the resultingreaction mixture.

13. A process for the preparation of a polycarbonate resin whichcomprises (1) reacting together from about 10 to about 90 weight percentof a fatty oil and from about 90 to about 10 weight percent of abisphenol selected from the group consist ng of bishpenols having thestructure HO OH Rn R'n in which R is a member of the group consisting ofthe divalent alkane and saturated alicyclic radicals and the divalentaryl and aralkyl radicals containing only aromtic unsaturation, R is arnonovalent alkane radical and n is an integer from 0 to 4, and thederivatives of those bisphenols which contain halogen attached to carbonin an aromatic ring at a temperature of between the melt- 11 p ing pointand the boiling point of said bisphenol, (2) reacting said reactionproduct (1) with at least 0.1 mol of phosgen'e per mol of bisphenol in asolution containing at 1 least one mol of pyridineper mol of bisphenol,and(3) recovering the polycarbonate resin from the resulting reactionmixture. f v

14. A process for the preparation of a polycarbonate resin whichcomprises (1)' reacting together from about 10 to about 90 weightpercent of a fatty oil and from about 90 to about 10 weight percent of abisphenol selected from the group consisting of bisphenols having thestructure t2 7 ing said reaction product (1) with at'least 0.1 mol ofphosgene per mol of bisphenol' in an aqueous alkaline medium, and (3)recovering the polycarbonate resin from the resulting reaction mixture.

7 15. A process according to claim 14 wherein said reaction (2) isconducted in the presence of a quaternary ammonium compound as acatalyst.

16. A process according to claim 15 wherein said reaction (2) isconducted in the presence of an inert solvent which is immiscible inwater.

17. A process according to claim 16 wherein said bisphenol is2,2-(4,4'-dihydroxy-diphenyl)propane.

18. A process according to claim'16 wherein said his phenol is1,4-(4,4-dihydroxy-dicumyl)-benzene.

19. A process according to claim 17 wherein said fatty oil is dehydratedcastor oil.

20. A process according to claim 17 wherein said fatty oil is coconutoil.

References Cited in the file of this'patent UNITED STATES PATENTS2,588,821 Geiger Mar. 29,1955 3,028,365 Schnell et al. Apr. 3', 19623,030,331

Goldberg Apr. 17, 1962

1. A POLYCARBONATE RESIN PRODUCED BY REACTING (1) AN ESTER FORMINGDERIVATIVE OF CARBONIC ACID SELECTED FROM THE GROUP CONSISTING OFPHOSGENE AND A CARBONIC ACID DIESTER, AND (2) THE REACTION PRODUCTOBTAINED BY HEATING A MIXTURE OF FROM ABOUT 10 TO ABOUT 90 WEIGHTPERCENT OF A FATTY OIL AND FROM ABOUT 90 TO ABOUT 10 WEIGHT PERCENT OF ABISPHENOL SELECTED FROM THE GROUP CONSISTING OF BISPHENOLS HAVING THESTRUCTURE